CN104032297A - Film forming liquid of aluminum alloy surface conversion film as well as preparation method and application thereof - Google Patents
Film forming liquid of aluminum alloy surface conversion film as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN104032297A CN104032297A CN201410242562.7A CN201410242562A CN104032297A CN 104032297 A CN104032297 A CN 104032297A CN 201410242562 A CN201410242562 A CN 201410242562A CN 104032297 A CN104032297 A CN 104032297A
- Authority
- CN
- China
- Prior art keywords
- forming liquid
- aluminum alloy
- film forming
- conversion film
- alloy surface
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention relates to a preparation method and application of film forming liquid of an aluminum alloy surface conversion film. The preparation method of the film forming liquid is characterized by comprising the following steps: (11) magnesium salt and ammonium salt are dissolved by using de-ionized water, and are fully stirred to obtain a component a; (12) anionic compound solution is added in the component a to obtain pH value modifier; (13) one or several of sodium hydroxide, potassium hydroxide or ammonium hydroxide is dissolved by using the de-ionized water to obtain the pH value modifier; and (14) the pH value modifier is dripped in the pH value modifier, and is fully stirred to obtain the film forming liquid. The aluminum alloy surface conversion film is prepared by using the film forming liquid; and a preparation process of the conversion film comprises the following steps: (51) the film forming liquid is diluted to working solution; (52) the surface of aluminum alloy is pre-treated; (53) the aluminum alloy is treated in the working solution; and (54) the surface of the aluminum alloy is washed by water, and is dried.
Description
Technical field
The present invention relates to the invention belongs to metal finishing and anticorrosion technique field, especially a kind of preparation method and application of film forming liquid of aluminum alloy surface conversion film.
Background technology
In recent years, in order to tackle the lightweight requirements of the rail vehicle such as subway, high ferro structure, aluminium alloy vehicle gets most of the attention, and has advanced the process being transformed to aluminum alloy materials by stainless material in the past, has expanded the application of aluminium alloy.But aluminium alloy autoxidation film is thinner, add that long-term severe physical environment corrodes, and is prone to the large problems such as burn into variable color as the aluminum alloy surface of car body external application plate.Adopt application techniques can improve the solidity to corrosion of aluminum alloy surface, but aluminium alloy after application has lost self original metalluster, and under the severe physical environment such as dust storm scraping, coating is easily peeled off, and causes damage taking painting defect as starting point expands.And aluminium alloy do not adopt the application such as putty, paint without application techniques, reduced welding wire, the damage of gas to alloy matrix aluminum, not only greatly reduce costs, and reduced car body weight, reduce energy consumption, greatly promoted the development of aluminum alloy surface treatment technology.
In aluminum alloy surface treatment technology, chemical conversion processing cost is low, and technique is simple, studies and is most widely used.The main chromic salt processing that adopts is processed in traditional aluminum alloy surface chemical conversion, but the sexavalent chrome in chromic salt, environment is had to serious pollution, human body is had to carcinogenic harm, also can bring serious follow-up pollution to environment, WEES and RoHS instruction have strictly limited the use of chromic salt, and its application is subject to strict restriction.Therefore, many environment-friendly chromium-free conversion films arise at the historic moment, as molybdate film, permanganate film, fluorine pick hydrochlorate film, organic inorganic hybridization film etc.But the appearance color of above-mentioned these conversion films, solidity to corrosion, also do not reach the requirement without the aluminum alloy surface conversion film of application techniques far away.
Japan started to take the lead in from 1994 to without application aluminum alloy surface Processing Technology Research, open (JP 7-278838 of a series of patents about the manufacture method without application aluminum or aluminum alloy member, purging method, stain resistance raising and surface-coated method, JP 07-278839, JP 07-278899, JP 08-74066, JP 08-141889).And China and other countries also seldom disclose the Patents of invention aluminum alloy surface without application conversion film technology at present.
In recent years, hydrotalcite-based compound (Layered Double Hydroxides, be abbreviated as LDHs) due to its unique textural property, main body laminate and the interlayer anion of hydrotalcite link by hydrogen bond, make interlayer anion kind, in relative broad range, modulation can occur, corrodibility negatively charged ion in environment can and rest on hydrotalcite layers with interlayer anion exchange, has avoided directly contacting with matrix, thereby has played the effect of slowing down corrosion.Hydrotalcite has the characteristic of surface hydrophobicity simultaneously, and the advantages such as raw material easily obtains, asepsis environment-protecting are had good prospect by it at corrosion field.At present hydrotalcite film in the applied research in metal corrosion and protection field still in the starting stage.As the people such as Zhang Fazhi have invented a kind of method of preparing erosion resistance hydrotalcite film at aluminium and aluminum alloy surface growth in situ at patent CN101285185A, conversion film prepared by this method has certain anti-corrosion capability, but the anticorrosion life-span of conversion film is shorter.Invention growth in situ calixarene intercalation hydrotalcite film in aluminium substrate and preparation method thereof in patent CN102650065A, the film of preparation and the reactive force of substrate are strong, difficult drop-off, but this preparation method's treatment time is long, and process energy consumption is large, and cost is high.
Given this present invention is proposed.
Summary of the invention
Object of the present invention, for overcoming the deficiencies in the prior art, provides a kind of film forming liquid of aluminum alloy surface conversion film.
Another object of the present invention is for providing a kind of preparation method of film forming liquid of aluminum alloy surface conversion film.
Another object of the present invention is for providing a kind of application of film forming liquid of aluminum alloy surface conversion film.
In order to realize this object, the present invention adopts following technical scheme: a kind of film forming liquid of aluminum alloy surface conversion film, described film forming liquid is made up of magnesium salt solution, ammonium salt solution, anionic compound solution and pH value conditioning agent, the content of the magnesium ion in described film-forming soln is 0.8～10g/L, the content of ammonium radical ion is 2.8～20g/L, the content of anionic compound is 0～5g/L, and the pH value of described film-forming soln is 7.0～12.5.
In described magnesium salt solution, magnesium salts is the soluble inorganic salt containing magnesium ion, and magnesium salts is one or more in magnesium nitrate, magnesium sulfate or magnesiumcarbonate;
In described ammonium salt solution, ammonium salt is the soluble inorganic salt containing ammonium radical ion, and ammonium salt is one or more in ammonium nitrate, ammonium sulfate or ammonium chloride;
Described anionic compound is one or both in m-phthalic acid or sodium polyphosphate;
Described pH value conditioning agent is one or more the aqueous solution in sodium hydroxide, potassium hydroxide or ammoniacal liquor.
A preparation method for the film forming liquid of aluminum alloy surface conversion film, comprises the following steps:
(11) by magnesium salts, ammonium salt deionized water dissolving, fully stir, obtain component a;
(12) by one or more the use deionized water dissolvings in sodium hydroxide, potassium hydroxide or ammoniacal liquor, obtain pH value conditioning agent;
(13) pH value conditioning agent is splashed in component a, fully stir, to pH value be 7.0～12.5, obtain film forming liquid.
In step (11) component a, can also add anionic compound additive.
In described film forming liquid, the content of ammonium salt is 8～35g/L; The content of ammonium salt is 5～30g/L; The content of anionic compound additive is 0～10g/L.
In described film forming liquid, magnesium ion is 1:4～1:2 with the molar mass ratio of ammonium radical ion.
An application for the film forming liquid of aluminum alloy surface conversion film, is characterized in that: use this film forming liquid to prepare aluminum alloy surface conversion film, the preparation technology of conversion film comprises the following steps:
(51) film forming liquid is diluted to working fluid;
(52) aluminum alloy surface pre-treatment;
(53) aluminium alloy is processed in working fluid;
(54) aluminum alloy surface is washed and dried.
The described working fluid of step (51) is the solution obtaining after film forming liquid is diluted to 1～5 times.
Processing in step (53) is aluminium alloy to be placed in to working fluid carry out chemical conversion processing, and the treatment time is 10 minutes～6 hours, and preferably 20 minutes～4 hours, treatment temp was 40 DEG C～90 DEG C.
Described in step (54), drying is that aluminium alloy is toasted 5～30 minutes at 50～120 DEG C.
Adopt after technical solutions according to the invention, bring following beneficial effect:
The film forming liquid water white transparency of the aluminum alloy surface conversion film that 1, prepared by the present invention, does not relate to chromium element and phosphoric, environmental protection, good stability, formula is simple, and cost is low, and film forming liquid can be recycled for a long time, can be used as the surrogate of chromic salt processing for the final corrosion-resistant coating of aluminium alloy.
2, aluminum alloy surface conversion film preparation technology flow process of the present invention is simple, and preparation time is not long, and energy consumption is low, and cost is low.
3, the aluminum alloy surface conversion film that prepared by the present invention has hydrotalcite-like compound, conversion film is fine and close continuously, strong with alloy matrix aluminum bonding force, there is excellent alkali resistance and high corrosion resistance, by the neutral salt spray test test of 168 hours-480 hours, meet the requirement without application aluminum alloy surface high anti-corrosion conversion film.
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Brief description of the drawings
The scanning electron microscope sem figure of Fig. 1 embodiment 1 conversion film;
The scanning electron microscope sem figure of Fig. 2 embodiment 2 conversion films;
The scanning electron microscope sem figure of Fig. 3 embodiment 3 conversion films;
The scanning electron microscope sem figure of Fig. 4 embodiment 4 conversion films;
The scanning electron microscope sem figure of Fig. 5 comparative example 1 conversion film;
The scanning electron microscope sem figure of Fig. 6 comparative example 2 conversion films;
The electrochemistry Tafel polarization curve comparison diagram of the conversion film of Fig. 7 embodiment 1 after soaking;
The electrochemistry Tafel polarization curve comparison diagram of the conversion film of Fig. 8 embodiment 2 after the different conversion processing time;
Fig. 9 embodiment 1, embodiment 2, embodiment 3 and comparative example 1, comparative example 2 make the electrochemistry Tafel polarization curve comparison diagram of aluminum alloy surface conversion film;
Figure 10 comparative example 1 and embodiment 1 make the electrochemistry Tafel polarization curve comparison diagram of aluminum alloy surface conversion film;
Figure 11 comparative example 2 and embodiment 1 make the electrochemistry Tafel polarization curve comparison diagram of aluminum alloy surface conversion film;
The conversion film making in Figure 12 embodiment 1 is placed the digital photograph figure of 0 hour (12a), 480 hours (12b) at corrosive environment (neutral salt spray test);
The conversion film making in Figure 13 embodiment 2 is placed the digital photograph figure of 0 hour (13a), 480 hours (13b) at corrosive environment (neutral salt spray test);
The conversion film making in Figure 14 embodiment 3 is placed the digital photograph figure of 0 hour (14a), 196 hours (14b) at corrosive environment (neutral salt spray test);
The conversion film making in Figure 15 embodiment 4 is placed the digital photograph figure of 0 hour (15a), 168 hours (15b) at corrosive environment (neutral salt spray test);
The conversion film making in Figure 16 comparative example 1 is placed the digital photograph figure of 0 hour (16a), 168 hours (16b) at corrosive environment (neutral salt spray test);
The conversion film making in Figure 17 comparative example 2 is placed the digital photograph figure of 0 hour (17a), 120 hours (17b) at corrosive environment (neutral salt spray test).
Embodiment
Below in conjunction with specific embodiment, the present invention is further explained and is illustrated, but the present invention is not limited to the scope described in embodiment.
The method that the present invention carries out correlation detection to Conversion Coatings on Aluminum Alloys rete comprises:
1. electro-chemical test: the electrochemical workstation CHI604D that adopts Shanghai Chen Hua equipment company.The electrochemistry curve of measuring respectively different conversion films, judges its erosion resistance with this.
2. micro-structural test: adopt the Japanese PHILIPS XL-30 of company type scanning electronic microscope (SEM) to observe aluminum alloy surface conversion film microtexture.
3. alkali resistance test: adopt 3%NaOH solution for soaking medium.Soaking 30s conversion film surface has or not obvious bubble and conversion film to have or not to fade;
4. saline soak test: adopt 5%NaCl solution for soaking medium.Soak and after 30 days, see test plate (panel) conversion film rete has or not and come off, it is unchanged etc. that color has.
5. resistance to drop performance: adopt potassium bichromate solution (hydrochloric acid 25ml, potassium bichromate 3g, distilled water 75ml preparation) to measure the resistance to drop corrosive nature of aluminium surface conversion coating;
6. neutral salt spray test: the solidity to corrosion of measuring conversion film with reference to the standard neutral salt spray test of GB/T10125-1997.
The film forming liquid of a kind of aluminum alloy surface conversion film of the present invention, described film forming liquid is made up of magnesium salt solution, ammonium salt solution, anionic compound solution and pH value conditioning agent, the content of the magnesium ion in described film-forming soln is 0.8～10g/L, the content of ammonium radical ion is 2.8～20g/L, the content of anionic compound is 0～5g/L, and the pH value of described film-forming soln is 7.0～12.5.
Magnesium ion content is too high, and film forming speed is fast, and the fine and close not solidity to corrosion of rete declines, and also causes reagent waste.Magnesium ion content is too low, and hydrotalcite-like compound generates insufficient, and rete is sufficiently complete, and continuously fine and close not, solidity to corrosion reduces.
In described magnesium salt solution, magnesium salts is the soluble inorganic salt containing magnesium ion, and magnesium salts is one or more in magnesium nitrate, magnesium sulfate or magnesiumcarbonate;
In described ammonium salt solution, ammonium salt is the soluble inorganic salt containing ammonium radical ion, and ammonium salt is one or more in ammonium nitrate, ammonium sulfate or ammonium chloride;
Described anionic compound is one or both in m-phthalic acid or sodium polyphosphate;
Described pH value conditioning agent is one or more the aqueous solution in sodium hydroxide, potassium hydroxide or ammoniacal liquor.
The preparation method of the film forming liquid of a kind of aluminum alloy surface conversion film of the present invention, comprises the following steps:
(11) by magnesium salts, ammonium salt deionized water dissolving, fully stir, obtain component a;
(12) by one or more the use deionized water dissolvings in sodium hydroxide, potassium hydroxide or ammoniacal liquor, obtain pH value conditioning agent;
(13) pH value conditioning agent is splashed in component a, fully stirs, to pH value be 7.0～12.5, preferably 7.5～9.5, obtain film forming liquid.Because present inventor's great many of experiments shows, in the time of pH >=9.5, film forming speed is fast, and conversion film forms the inhomogeneous outward appearance that affects, and rete is continuously fine and close not, and solidity to corrosion reduces.And in the time of pH≤7.5, treatment solution basicity is inadequate, be difficult to " activation " alloy matrix aluminum and produce Al3+, the formation speed of conversion film is slow, and rete covers not exclusively matrix surface, and Corrosion Protection is poor.
In step (11) component a, can also add anionic compound additive.
In described film forming liquid, the content of ammonium salt is 8～35g/L; The content of ammonium salt is 5～30g/L; The content of anionic compound additive is 0～10g/L.
In described film forming liquid, magnesium ion is 1:4～1:2 with the molar mass ratio of ammonium radical ion.
The application of the film forming liquid of a kind of aluminum alloy surface conversion film of the present invention, is characterized in that: use this film forming liquid to prepare aluminum alloy surface conversion film, the preparation technology of conversion film comprises the following steps:
(51) film forming liquid is diluted to working fluid;
(52) aluminum alloy surface pre-treatment;
(53) aluminium alloy is processed in working fluid;
(54) aluminum alloy surface is washed and dried.
The described working fluid of step (51) is the solution obtaining after film forming liquid is diluted to 1～5 times.
Processing in step (53) is aluminium alloy to be placed in to working fluid carry out chemical conversion processing, treatment time is 10 minutes～6 hours, preferably 20 minutes～4 hours, great many of experiments shows, time is too short, conversion film forms not exclusively, and hydrotalcite-like compound is loose porous, and the solidity to corrosion of rete is low.Time is oversize, and conversion film forms complete not regrowth, and film heavily increases, and the bonding force of rete and matrix declines, and corrosion resisting property reduces, and cost energy consumption is high.Excess Temperature, conversion film speed is fast, and rete is more loose, and corrosion resistance nature declines, and cost is large, and energy consumption is high.Treatment temp is 40 DEG C～90 DEG C, preferably 65 DEG C～85 DEG C.Temperature is too low, and conversion film speed is slow, and required transformation time is long, and rete covers not exclusively matrix surface, and rete is combined insecure with matrix, and corrosive nature is low.
Described in step (54), drying is that aluminium alloy is toasted 5～30 minutes at 50～120 DEG C.
The method is applied in aluminum alloy surface, for 5000 be especially and 6000 line aluminium alloys, can form one deck matrix look, high anti-corrosion in aluminum alloy surface by the method, the conversion film of the even continuous hydrotalcite-like compound of excellent alkali resistance, easy recovery that treatment solution is pollution-free, conversion treatment process is simple, workable, without carrying out follow-up application processing, process costs is low, whole flow process environmental protection.
Embodiment 1
The preparation of film forming liquid:
(1) preparation of component a: take magnesium nitrate hexahydrate 15.37g, ammonium nitrate 19.21g, adopts 400g deionized water dissolving, is stirred well to it and dissolves completely, adopt deionized water by this solution dilution to 1L.(2) preparation of pH value conditioning agent: first weighing sodium hydroxide 5g, adopt 100mL deionized water dissolving, be stirred well to it and dissolve completely.(3) then with glue head dropper, pH value conditioning agent is dropwise added to component a, stir on dropping limit, limit, in the time of pH value to 7.5, stops dripping.(4) get above-mentioned solution 500mL, adopt deionized water to be diluted to 1L, more dropwise add pH value conditioning agent regulator solution pH value to 8.0 to obtain the transparent working fluid of good stability.
The preparation of conversion film:
Prepare 5083 aluminium alloy test pieces, aluminium alloy test piece is immersed in homemade acidic degreasing liquid 3 minutes, after deionization washing twice, immerse the above-mentioned temperature preparing and be in the work for the treatment of liquid of aluminum alloy surface high anti-corrosion conversion film of 80 DEG C 2 hours, take out test piece naturally dries after deionization washing, in heated oven, dry 10 minutes at 120 DEG C, cooling naturally drying 24 hours, obtains embodiment 1 conversion film.
The embodiment of the present invention 1 conversion film structure and Performance Detection are analyzed as follows:
The conversion film of embodiment 1 is colourless, and through scanning electron microscope test (as Fig. 1), aluminum alloy surface conversion film is the petal-shaped structure of nearly 350nm, and rule stack is netted, and loose porous, rete is continuous and fine and close, is typical hydrotalcite-like compound.Conversion film soaks respectively after 0 day, 1 day, 3 days, 7 days and detects its electrochemistry Tafel polarization curve (as Fig. 7) through electrochemical workstation in 5%NaCl solution, and result shows that the corrosion current density of soaking 0 day is 1.940 × 10
-7a/cm
2, the corrosion current density of soaking in corrosive environment 5%NaCl solution after 1 day is 3.514 × 10
-9a/cm
2, the corrosion current density of soaking in corrosive environment 5%NaCl solution after 3 days is 1.209 × 10
-5a/cm
2, the corrosion current density of soaking in corrosive environment 5%NaCl solution after 7 days is 2.937 × 10
-7a/cm
2.The neutral salt spray test result (as Figure 12) of conversion film show embodiment 1 aluminium alloy hydrotalcite-like compound conversion film in corrosive environment, place 196 hours place before (12a) there is little corrosion pit (counting≤5), after placing 480 hours (12b), little corrosion pit still exists, but corroded area does not expand, there is not continuing corrosion, conversion film excellent corrosion-proof performance.
Embodiment 2:
The preparation of film forming liquid:
(1) preparation of component a: take magnesium nitrate hexahydrate 25.61g, ammonium nitrate 24.13g, adopts 500g deionization to dissolve, and is stirred well to it and dissolves completely, adopt deionized water by this solution dilution to 1L.(2) preparation of pH value conditioning agent: weighing sodium hydroxide 7g, adopts 100mL deionized water dissolving, is stirred well to it and dissolves completely.(3) with glue head dropper, pH value conditioning agent is dropwise added to component a, stir on dropping limit, limit, in the time of pH value to 8.0, stops dripping.(4) get above-mentioned solution 500mL, adopt deionized water to be diluted to 1L, more dropwise add pH value conditioning agent regulator solution pH value to 8.5 to obtain the transparent working fluid of good stability.
The preparation of conversion film:
Prepare the test piece of 6N01 aluminium alloy, aluminium alloy test piece is immersed in homemade acidic degreasing liquid 3 minutes, after deionization washing twice, immerse deionization boiling water 5 minutes, taking out test piece, to immerse the above-mentioned temperature preparing in 30 minutes be in the work for the treatment of liquid of aluminum alloy surface high anti-corrosion conversion film of 70 DEG C 1 hour, takes out test piece and naturally dry after deionization washing, in 100 DEG C of baking ovens, dries 10 minutes, cooling naturally drying 24 hours, obtains embodiment 2 conversion films.
The embodiment of the present invention 2 conversion film structures and Performance Detection are analyzed as follows:
The conversion film of embodiment 2 is colourless, and through scanning electron microscope test (as Fig. 2), aluminum alloy surface conversion film is the petal-shaped structure of nearly 500nm, closely stack, few hole, rete is roughly smooth, small part is piled up and is flower shape, continuous and fine and close, is hydrotalcite-like compound.Compared with the finer and close few hole of the pattern of embodiment 1 conversion film, reason may be that the boiling water before conversion processing is washed processing " activation " alloy matrix aluminum greatly, obtains presoma conversion film, then obtains fine and close continuous hydrotalcite-like compound conversion film through conversion processing.Electricity consumption chemistry Tafel polarization curve is analyzed (as Fig. 8), and the corrosion current density that shows the hydrotalcite-like compound conversion film that in embodiment 2, aluminium alloy obtains after 1 hour in conversion processing is 5.342 × 10
-8a/cm
2, the corrosion current density of the hydrotalcite-like compound conversion film obtaining after 3 hours in conversion processing is 1.109 × 10
-8a/cm
2, the corrosion current density of the hydrotalcite-like compound conversion film obtaining after 5 hours in conversion processing is 6.571 × 10
-9a/cm
2, the corrosion current density of the hydrotalcite-like compound conversion film obtaining after 7 hours in conversion processing is 7.180 × 10
-9a/cm
2.The conversion film that the embodiment of the present invention 2 aluminium alloys obtain after 1 hour in conversion processing has certain solidity to corrosion, the corrosion current density of the conversion film that conversion processing obtained after 3 hours reduces nearly 5 times, illustrate that the conversion processing time is longer, the solidity to corrosion of conversion film improves, reason may be that conversion film after houghite particle nucleation, passes through certain crystallization time in formation hydrotalcite-like compound process, and amorphous particle is slowly grown up, rete is more complete, and solidity to corrosion improves.The corrosion current density of the conversion film that conversion processing obtains after 5 hours, 7 hours is close, reduces nearly order of magnitude compared with the conversion processing corrosion current density of 1 hour, illustrates that the conversion processing time is longer, the solidity to corrosion of conversion film improves, reason may be under same temperature, and the conversion processing time is longer, and crystallization process is longer, the crystal grain of houghite is grown up gradually, arrived certain hour, grain-size has stopped growing up, and it is complete that crystal phase structure is tending towards, rete is finer and close, and solidity to corrosion is better.Neutral salt spray test result (Figure 13) show embodiment 2 conversion films in corrosive environment, place after 480 hours (13b) with place before (13a) substantially do not change, conversion film does not substantially fade and peels off, and conversion film excellent corrosion-proof performance is described.
Embodiment 3:
The preparation of film forming liquid:
(1) preparation of component a: take magnesium nitrate hexahydrate 23.05g, ammonium nitrate 28.82g, adopts 800g deionization to dissolve, and is stirred well to it and dissolves completely, adopt deionized water by this solution dilution to 900mL.(2) take m-phthalic acid sodium 8g, adopt 100mL deionized water dissolving, be stirred well to it and dissolve completely, added in component a, be fully uniformly mixed.(3) weighing sodium hydroxide 8g, adopts 100mL deionized water dissolving, is stirred well to it and dissolves completely, obtains pH adjusting agent.(4) with glue head dropper, pH adjusting agent is dropwise added to pH value conditioning agent, in the time of the pH value to 9.5 of pH value conditioning agent, stop dripping.(4) get above-mentioned solution 500mL, adopt deionized water to be diluted to 1L, more dropwise add pH value conditioning agent regulator solution pH value to 9.5, obtain the transparent working fluid of good stability.
The preparation of conversion film:
Prepare 6063 aluminium alloy test pieces, aluminium alloy test piece is immersed in homemade acidic degreasing liquid 3 minutes, after deionization washing twice, immerse deionization boiling water 5 minutes, taking out test piece, to immerse the above-mentioned temperature preparing be in the work for the treatment of liquid of aluminum alloy surface high anti-corrosion conversion film of 60 DEG C 2 hours, takes out test piece and naturally dry after deionization washing, in 80 DEG C of baking ovens, dries 5 minutes, take out cooling naturally drying 24 hours, obtain embodiment 3 hydrotalcite-like compound conversion films.
The embodiment of the present invention 3 conversion film structures and Performance Detection are analyzed as follows:
Scanning electronic microscope result (Fig. 3) shows that embodiment 3 aluminum alloy surface conversion films are the narrow and small blade-like structure of nearly 300nm, is uniformly distributed, and rete is smooth, continuous and fine and close, is hydrotalcite-like compound.Pattern sheet structure size compared with embodiment 1 and embodiment 2 conversion films is less, distribute more even, reason may be that a small amount of m-phthalic acid additive can make aluminium alloy matrix surface charge distribution more even on the one hand, crystallization is more careful, the hydrotalcite-like compound generating is more even, m-phthalic acid radical ion also can be intercalation into hydrotalcite structure smoothly as negatively charged ion on the other hand, generates the blade-like hydrotalcite structure of size homogeneous.Electricity consumption chemistry Tafel polarization curve is analyzed (Fig. 9), and the corrosion current density that shows embodiment 3 Conversion Coatings on Aluminum Alloys is 1.082 × 10
-7a/cm
2corrosion current density compared with embodiment 1 Conversion Coatings on Aluminum Alloys is close, compared with high nearly 1 order of magnitude of the corrosion current density of embodiment 2 Conversion Coatings on Aluminum Alloys, show that m-phthalic acid sodium can suitably improve the solidity to corrosion of rete as anionic additive, reason may be that the negatively charged ion that the hydrolysis of m-phthalic acid sodium produces can be intercalation in hydrotalcite structure, make hydrotalcite structure finer and close, the solidity to corrosion of rete improves compared with intercalation money.Neutral salt spray test result (Figure 14) shows to start to occur brown filiform corrosion product, corroded area approximately 5% left and right after (14a) before embodiment 3 Conversion Coatings on Aluminum Alloys are placed 196 hours (14b) and placed in corrosive environment.The conversion film that embodiment 3 aluminium alloy hydrotalcite-like compounds are described has certain solidity to corrosion.
Embodiment 4:
The preparation of film forming liquid:
(1) preparation of component a: take magnesium nitrate hexahydrate 30.74g, ammonium nitrate 19.21g, adopts 900g deionization to dissolve, and is stirred well to it and dissolves completely, adopt deionized water by this solution dilution to 1000mL.(2) take sodium polyphosphate 11g, adopt 200mL deionized water dissolving, be stirred well to it and dissolve completely, added in component a, be fully uniformly mixed.(3) take ammoniacal liquor 10g, adopt 150mL deionized water dissolving, be stirred well to it and dissolve completely, obtain pH adjusting agent.(4) with glue head dropper, pH adjusting agent is dropwise added to pH value conditioning agent, in the time of the pH value to 9.0 of pH value conditioning agent, stop dripping.(4) get above-mentioned solution 500mL, adopt deionized water to be diluted to 1L, more dropwise add pH value conditioning agent regulator solution pH value to 9.3, obtain the transparent working fluid of good stability.
The preparation of conversion film:
Prepare the test piece of 6N01 aluminium alloy, aluminium alloy test piece is immersed in homemade acidic degreasing liquid 3 minutes, after deionization washing twice, immerse deionization boiling water 5 minutes, taking out test piece, to immerse the above-mentioned temperature preparing be in the work for the treatment of liquid of aluminum alloy surface high anti-corrosion conversion film of 60 DEG C 20 minutes, takes out test piece and naturally dry after deionization washing, in 90 DEG C of baking ovens, dries 10 minutes, take out cooling naturally drying 24 hours, obtain embodiment 4 hydrotalcite-like compound conversion films.
The embodiment of the present invention 4 conversion film structures and Performance Detection are analyzed as follows:
Scanning electronic microscope result (Fig. 4) shows that embodiment 4 aluminum alloy surface conversion films are bilayer structure, continuously fine and close near one deck of matrix, the careful structure with honeycomb hole of crystallization, also has the structures of a lot of bits sheets above it, random and loosely cover in the first layer structure.Pattern sheet structure compared with embodiment 1, embodiment 2, embodiment 3 conversion films has marked difference, conversion film is bilayer structure, but near matrix the first layer structure continuously with honeycomb hole shape, the wood chip shape short texture covering above the first layer distributes, the not fine and close compactness of whole conversion film structure.Reason may be that a negatively charged ion part for sodium polyphosphate hydrolysis has been intercalation into hydrotalcite structure, the remaining negatively charged ion that there is no intercalation is attached to its surface, may be because the phosphate anion segment of sodium polyphosphate hydrolysis is longer, molecular volume is larger, so can make hydrotalcite structure more not add the more loose porous of sodium polyphosphate after being intercalation into hydrotalcite structure.Electricity consumption chemistry Tafel polarization curve is analyzed (Fig. 9), shows that the corrosion current density of embodiment 4 (Fig. 9-4) Conversion Coatings on Aluminum Alloys is 3.659 × 10
-6a/cm
2compared with the corrosion current density of embodiment 1 (Fig. 9-1) and embodiment 3 (Fig. 9-3) Conversion Coatings on Aluminum Alloys nearly order of magnitude that raise, compared with the corrosion current density of embodiment 2 (Fig. 9-2) Conversion Coatings on Aluminum Alloys nearly two orders of magnitude that raise.Show that sodium polyphosphate does not actively affect the solidity to corrosion of rete as anionic additive, reason may be that the negatively charged ion part after sodium polyphosphate hydrolysis is intercalation in hydrotalcite structure, a remaining part is attached to its surface, non-quantitative and unordered intercalation make conversion film loose porous with arranging, and therefore solidity to corrosion reduces.Neutral salt spray test result (Figure 15) shows to start to occur brown filiform corrosion, corroded area approximately 5% left and right after (15a) before embodiment 4 Conversion Coatings on Aluminum Alloys are placed 168 hours (15b) and placed in corrosive environment.The conversion film that embodiment 4 aluminium alloy hydrotalcite-like compounds are described has certain solidity to corrosion.
Comparative example 1: the preparation of aluminum alloy surface chromate conversion coating
For the treatment process difference of the present invention relatively and traditional chromaking technology, the present invention has adopted following comparative example.
The D-3 passivator that phosphorization technology company limited of gulf Xiaxin provides, is mainly made up of chromic salt.------Passivation Treatment---washing---is dried in washing in technical process: aluminum alloy surface pre-treatment.Passivating solution adopts the preparation of 20%D-3 passivator, processes 10 minutes-20 minutes at 50 DEG C.Gained conversion film is chromate conversion coating.
Comparative example 1 conversion film structure and Performance Detection are analyzed as follows:
Scanning electronic microscope result (Fig. 5) shows comparative example 1 Conversion Coatings on Aluminum Alloys, and heap cloud is vaporific in the form of sheets, and size distribution is inhomogeneous, and conversion film is fine and close continuously, has very big difference compared with the conversion film microtexture of embodiment 1.Electricity consumption chemistry Tafel polarization curve is analyzed (Figure 10), and the corrosion current density that shows comparative example 1 Conversion Coatings on Aluminum Alloys (a) is 2.115 × 10
-5a/cm
2, want high nearly 2 orders of magnitude compared with the corrosion current density of embodiment 1 (b).The resistance to spot test time is 240 seconds, and alkaline resistance test occurs that the time of a large amount of bubbles is 20 seconds.Neutral salt spray test result (Figure 16) shows to start to have thread brown corrosion product to occur after (a) before aluminium alloy comparative example 1 Conversion Coatings on Aluminum Alloys is placed 168 hours (b) and placed in corrosive environment, shows that corrosion starts.Comparative example 1 conversion film is colourless.
Comparative example 2: the preparation of aluminum alloy surface vitrification film
For the relatively difference of the treatment process of the present invention and existing vitrification technology, the present invention has adopted following comparative example.
The JS-58 vitrified agent that phosphorization technology company limited of gulf Xiaxin provides, is mainly made up of zirconates.Technical process: aluminum alloy surface pre-treatment-washing-vitrification processing-washing-washing-dry.Vitrification liquid adopts the preparation of 2%-3%JS-58 vitrified agent, then to add 0.3 ‰ vitrified agent adjusting agents to regulate pH values be 4.4-5.2, processes 10 minutes-20 minutes at 50 DEG C, and gained conversion film is vitrification film.
Comparative example 2 conversion film structures and Performance Detection are analyzed as follows:
Scanning electronic microscope result (Fig. 6) shows that comparative example 2 Conversion Coatings on Aluminum Alloys are the withered riverbed shape of chapping, and has a large amount of gap crackles, has very big difference compared with the conversion film microtexture of embodiment 1.Electricity consumption chemistry Tafel polarization curve is analyzed (Figure 11), shows that the corrosion current density of comparative example 2 (a) Conversion Coatings on Aluminum Alloys is 1.810 × 10
-4a/cm
2, want high nearly 3 orders of magnitude compared with the corrosion current density of embodiment 1 (b).The resistance to spot test time is 68 seconds, and the alkaline resistance test time is that 30 seconds conversion films occur without bubble.Neutral salt spray test result (Figure 17) show aluminium alloy comparative example 2 Conversion Coatings on Aluminum Alloys in corrosive environment, place 120 hours (b) and place before after (a) color deepen comprehensively, present light brown corrosion product, show that corrosion starts.The inhomogeneous whiting look of comparative example 2 conversion film outward appearance.
Embodiment 1, embodiment 2, embodiment 3 and comparative example 1, comparative example 2 without application aluminum alloy surface conversion film Performance Ratio as table 1.
Table 1 embodiment 1, embodiment 2, embodiment 3, embodiment 4 and comparative example 1, comparative example 2 without application aluminum alloy surface conversion film performance comparison:
Table 1 result shows, embodiment 1, embodiment 2, embodiment 3 and embodiment 4 aluminum alloy surface conversion films are the matrix look of continuous uniform, resistance to seeing attractive in appearance, conversion film is hydrotalcite-like compound, the drop time can reach 189 seconds～and 320 seconds, neutral salt spray test can pass through 168 hours wherein, and embodiment 1 and embodiment 2 can pass through 480 hours neutral salt spray tests, have high anti-corrosion and excellent alkaline resistance properties.It can also be seen that compared with comparative example 1 and comparative example 2, although houghite conversion film film is heavy lower, but solidity to corrosion is better compared with chromate conversion coating and vitrification film, Tafel polarization curve corrosion current density is less, alkali resistance is more excellent, the neutral salt spray test time is longer, and this explanation houghite conversion film is having very wide application prospect without application aluminum alloy surface processing technology field.
Embodiment 5
A kind of film forming liquid of aluminum alloy surface conversion film described in the present embodiment, described film forming liquid is made up of magnesium salt solution, ammonium salt solution, anionic compound solution and pH value conditioning agent, the content of the magnesium ion in described film-forming soln is 0.8/L, the content of ammonium radical ion is 2.8/L, and the pH value of described film-forming soln is 7.0～12.5.
Film forming liquid water white transparency, does not relate to chromium element and phosphoric, environmental protection, and good stability, formula is simple, and cost is low, and film forming liquid can recycle for a long time, can be used as the surrogate of chromic salt processing for the final corrosion-resistant coating of aluminium alloy.
Adopt above-mentioned film forming liquid to be diluted to working fluid, aluminium alloy test piece is immersed in homemade acidic degreasing liquid 3 minutes, after deionization washing twice, immerse deionization boiling water 5 minutes, taking out test piece, to immerse the above-mentioned temperature preparing be in the work for the treatment of liquid of aluminum alloy surface high anti-corrosion conversion film of 60 DEG C 2 hours, takes out test piece and naturally dry after deionization washing, in 80 DEG C of baking ovens, dries 5 minutes, take out cooling naturally drying 24 hours, obtain hydrotalcite-like compound conversion film.
Conversion film is fine and close continuously, and alloy matrix aluminum bonding force is strong, has excellent alkali resistance and high corrosion resistance, by the neutral salt spray test test of 168 hours-480 hours, meets the requirement without application aluminum alloy surface high anti-corrosion conversion film.
Embodiment 6
The film forming liquid of a kind of aluminum alloy surface conversion film of the present invention, described film forming liquid is made up of magnesium salt solution, ammonium salt solution, anionic compound solution and pH value conditioning agent, the content of the magnesium ion in described film-forming soln is 10g/L, the content of ammonium radical ion is 20g/L, the content of anionic compound is 5g/L, and the pH value of described film-forming soln is 12.5.
Film forming liquid water white transparency, does not relate to chromium element and phosphoric, environmental protection, and good stability, formula is simple, and cost is low, and film forming liquid can recycle for a long time, can be used as the surrogate of chromic salt processing for the final corrosion-resistant coating of aluminium alloy.
Adopt above-mentioned film forming liquid to be diluted to working fluid, aluminium alloy test piece is immersed in homemade acidic degreasing liquid 3 minutes, after deionization washing twice, immerse deionization boiling water 5 minutes, taking out test piece, to immerse the above-mentioned temperature preparing be in the work for the treatment of liquid of aluminum alloy surface high anti-corrosion conversion film of 60 DEG C 2 hours, takes out test piece and naturally dry after deionization washing, in 80 DEG C of baking ovens, dries 5 minutes, take out cooling naturally drying 24 hours, obtain hydrotalcite-like compound conversion film.
Conversion film is fine and close continuously, and alloy matrix aluminum bonding force is strong, has excellent alkali resistance and high corrosion resistance, by the neutral salt spray test test of 168 hours-480 hours, meets the requirement without application aluminum alloy surface high anti-corrosion conversion film.
Embodiment 7
The film forming liquid of a kind of aluminum alloy surface conversion film of the present invention, described film forming liquid is made up of magnesium salt solution, ammonium salt solution, anionic compound solution and pH value conditioning agent, the content of the magnesium ion in described film-forming soln is 5g/L, the content of ammonium radical ion is 10g/L, the content of anionic compound is 3g/L, and the pH value of described film-forming soln is 10.
Film forming liquid water white transparency, does not relate to chromium element and phosphoric, environmental protection, and good stability, formula is simple, and cost is low, and film forming liquid can recycle for a long time, can be used as the surrogate of chromic salt processing for the final corrosion-resistant coating of aluminium alloy.
Adopt above-mentioned film forming liquid to be diluted to working fluid, aluminium alloy test piece is immersed in homemade acidic degreasing liquid 3 minutes, after deionization washing twice, immerse deionization boiling water 5 minutes, taking out test piece, to immerse the above-mentioned temperature preparing be in the work for the treatment of liquid of aluminum alloy surface high anti-corrosion conversion film of 60 DEG C 2 hours, takes out test piece and naturally dry after deionization washing, in 80 DEG C of baking ovens, dries 5 minutes, take out cooling naturally drying 24 hours, obtain hydrotalcite-like compound conversion film.
Conversion film is fine and close continuously, and alloy matrix aluminum bonding force is strong, has excellent alkali resistance and high corrosion resistance, by the neutral salt spray test test of 168 hours-480 hours, meets the requirement without application aluminum alloy surface high anti-corrosion conversion film.
The foregoing is only the preferred embodiment of the present invention, it should be pointed out that for the ordinary skill in the art, without departing from the principles of the present invention, can also make various deformation and improvement, this also should be considered as protection scope of the present invention.
Claims (10)
1. the film forming liquid of an aluminum alloy surface conversion film, it is characterized in that: described film forming liquid is made up of magnesium salt solution, ammonium salt solution, anionic compound solution and pH value conditioning agent, the content of the magnesium ion in described film-forming soln is 0.8～10g/L, the content of ammonium radical ion is 2.8～20g/L, the content of anionic compound is 0～5g/L, and the pH value of described film-forming soln is 7.0～12.5.
2. the film forming liquid of a kind of aluminum alloy surface conversion film according to claim 1, is characterized in that: in described magnesium salt solution, magnesium salts is the soluble inorganic salt containing magnesium ion, and magnesium salts is one or more in magnesium nitrate, magnesium sulfate or magnesiumcarbonate;
In described ammonium salt solution, ammonium salt is the soluble inorganic salt containing ammonium radical ion, and ammonium salt is one or more in ammonium nitrate, ammonium sulfate or ammonium chloride;
Described anionic compound is one or both in m-phthalic acid or sodium polyphosphate;
Described pH value conditioning agent is one or more the aqueous solution in sodium hydroxide, potassium hydroxide or ammoniacal liquor.
3. a preparation method for the film forming liquid of aluminum alloy surface conversion film described in claim 1 or 2, is characterized in that: comprise the following steps:
(11) by magnesium salts, ammonium salt deionized water dissolving, fully stir, obtain component a;
(12) by one or more the use deionized water dissolvings in sodium hydroxide, potassium hydroxide or ammoniacal liquor, obtain pH value conditioning agent;
(13) pH value conditioning agent is splashed in component a, fully stir, to pH value be 7.0～12.5, obtain film forming liquid.
4. the preparation method of the film forming liquid of a kind of aluminum alloy surface conversion film according to claim 3, is characterized in that: in step (11) component a, can also add anionic compound additive.
5. the preparation method of the film forming liquid of a kind of aluminum alloy surface conversion film according to claim 4, is characterized in that: in described film forming liquid, the content of ammonium salt is 8～35g/L; The content of ammonium salt is 5～30g/L; The content of anionic compound additive is 0～10g/L.
6. the preparation method of the film forming liquid of a kind of aluminum alloy surface conversion film according to claim 5, is characterized in that: in described film forming liquid, magnesium ion is 1:4～1:2 with the molar mass ratio of ammonium radical ion.
7. an application for the film forming liquid of the arbitrary described aluminum alloy surface conversion film of claim 1-6, is characterized in that: use this film forming liquid to prepare aluminum alloy surface conversion film, the preparation technology of conversion film comprises the following steps:
(51) film forming liquid is diluted to working fluid;
(52) aluminum alloy surface pre-treatment;
(53) aluminium alloy is processed in working fluid;
(54) aluminum alloy surface is washed and dried.
8. the application of the film forming liquid of a kind of aluminum alloy surface conversion film according to claim 7, is characterized in that: the described working fluid of step (51) is the solution obtaining after film forming liquid is diluted to 1～5 times.
9. the application of the film forming liquid of a kind of aluminum alloy surface conversion film according to claim 7, it is characterized in that: the processing in step (53) is aluminium alloy to be placed in to working fluid carry out chemical conversion processing, treatment time is 10 minutes～6 hours, preferably 20 minutes～4 hours, treatment temp was 40 DEG C～90 DEG C.
10. the application of the film forming liquid of a kind of aluminum alloy surface conversion film according to claim 7, is characterized in that: described in step (54), drying is that aluminium alloy is toasted 5～30 minutes at 50～120 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410242562.7A CN104032297A (en) | 2014-06-03 | 2014-06-03 | Film forming liquid of aluminum alloy surface conversion film as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410242562.7A CN104032297A (en) | 2014-06-03 | 2014-06-03 | Film forming liquid of aluminum alloy surface conversion film as well as preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104032297A true CN104032297A (en) | 2014-09-10 |
Family
ID=51463285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410242562.7A Pending CN104032297A (en) | 2014-06-03 | 2014-06-03 | Film forming liquid of aluminum alloy surface conversion film as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104032297A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109072453A (en) * | 2016-04-12 | 2018-12-21 | 安加拉工业有限公司 | Remove the solution of various types deposit |
| CN112246577A (en) * | 2020-09-14 | 2021-01-22 | 中国第一汽车股份有限公司 | Steel-aluminum mixed flexible coating pretreatment process |
| CN114384002A (en) * | 2022-01-20 | 2022-04-22 | 江苏徐工工程机械研究院有限公司 | Method for detecting corrosion resistance of ceramic film and method for detecting quality of ceramic film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07278838A (en) * | 1994-04-12 | 1995-10-24 | Kobe Steel Ltd | Non-coated al or al alloy member, its production, cleaning method, method to improve contamination resistance, and method of surface coating |
| CN101054194A (en) * | 2006-04-12 | 2007-10-17 | 北京化工大学 | Ultra-hydrophobic lamellar dihydroxyl composite metal oxide thin film and preparing method thereof |
| CN101285185A (en) * | 2008-03-21 | 2008-10-15 | 北京化工大学 | Preparation method of corrosion resistant hydrotalcite-like film at surface of aluminum and aluminum alloy parts |
| CN102634835A (en) * | 2012-04-28 | 2012-08-15 | 北京化工大学 | Anticorrosive layered double-hydroxy composite metal hydroxide film and preparation method thereof |
-
2014
- 2014-06-03 CN CN201410242562.7A patent/CN104032297A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07278838A (en) * | 1994-04-12 | 1995-10-24 | Kobe Steel Ltd | Non-coated al or al alloy member, its production, cleaning method, method to improve contamination resistance, and method of surface coating |
| CN101054194A (en) * | 2006-04-12 | 2007-10-17 | 北京化工大学 | Ultra-hydrophobic lamellar dihydroxyl composite metal oxide thin film and preparing method thereof |
| CN101285185A (en) * | 2008-03-21 | 2008-10-15 | 北京化工大学 | Preparation method of corrosion resistant hydrotalcite-like film at surface of aluminum and aluminum alloy parts |
| CN102634835A (en) * | 2012-04-28 | 2012-08-15 | 北京化工大学 | Anticorrosive layered double-hydroxy composite metal hydroxide film and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 段雪 等: "《插层组装与功能材料》", 31 January 2007, 化学工业出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109072453A (en) * | 2016-04-12 | 2018-12-21 | 安加拉工业有限公司 | Remove the solution of various types deposit |
| CN112246577A (en) * | 2020-09-14 | 2021-01-22 | 中国第一汽车股份有限公司 | Steel-aluminum mixed flexible coating pretreatment process |
| CN114384002A (en) * | 2022-01-20 | 2022-04-22 | 江苏徐工工程机械研究院有限公司 | Method for detecting corrosion resistance of ceramic film and method for detecting quality of ceramic film |
| CN114384002B (en) * | 2022-01-20 | 2024-03-01 | 江苏徐工工程机械研究院有限公司 | Method for detecting corrosion resistance of ceramic film and method for detecting quality of ceramic film |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102766862B (en) | Treating fluid and method for preparing vanadium-zirconium composite conversion coatings with self-repairing performance on aluminum alloy surfaces through same | |
| CN102409332B (en) | Corrosion-contamination resistant chemical conversion agent and method for preparing chromium-free chemical conversion film | |
| CN102242358B (en) | Treatment solution and treatment method for preparing golden cryolite conversion film on surface of aluminum alloy | |
| TW402645B (en) | Process for forming a cobalt conversion coating on an aluminum or aluminum alloy substrate and the chemical conversion coating solution for use in the process | |
| CN103614717B (en) | Wear-resistance film layer prepared by a kind of Mg alloy surface hydrothermal method and preparation technology thereof | |
| CN105063598A (en) | Organic-inorganic residual heat blackening agent and preparation method thereof | |
| CN103614716B (en) | A kind of preparation method of environment-friendly type aluminum alloy surface rare earth inorganic compounding conversion film | |
| CN102925900A (en) | Alkaline chemical polishing solution and alkaline chemical polishing method | |
| CN102677038B (en) | Film forming solution for growing Mg-Al hydrotalcite film in situ on surface of magnesium alloy and application thereof | |
| CN105734574A (en) | Polishing solution | |
| CN105779988A (en) | Chromate-free passivation solution for electroplated zinc and passivation technology thereof | |
| CN104911577A (en) | Chromium-free alkaline passivation solution and passivation method for aluminum alloy | |
| CN101660153A (en) | Surface pretreatment agent before metal coating and preparation method and use method thereof | |
| CN103255405A (en) | Rare earth chromate-free passivation liquid for coating treatment of material and application of rare earth chromate-free passivation liquid | |
| CN108220940B (en) | A kind of normal temperature environment friendly aluminium alloy passivating solution, preparation method and application method | |
| CN104032297A (en) | Film forming liquid of aluminum alloy surface conversion film as well as preparation method and application thereof | |
| CN105063596A (en) | Treating fluid for chromate-free passivation of aluminum profiles before coating and preparation method thereof | |
| CN104451634B (en) | Aluminum and aluminum alloy passivation solution, preparation method and using method thereof | |
| CN103087627B (en) | A kind of metal aluminum alloy silane surface treatment agent and preparation method thereof | |
| CN101173354B (en) | Method for preparing trivalent chromium colorful passivation liquid for NdFeB Zinc-plated parts | |
| CN104342683A (en) | Magnesium alloy work-piece surface anti-corrosion conversion film treatment process | |
| CN103046037A (en) | High corrosion resistance trivalent chromium blue and white passivating liquid as well as preparation method and application of blue and white passivating liquid | |
| CN103614757B (en) | A kind of enclosure method of aluminum alloy surface porous-film rare earth | |
| CN101892476B (en) | Chemical oxidation treatment solution for aluminum alloy | |
| CN102409330A (en) | Chromium-free passivation solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: Jihongtan town Chengyang District Shandong city Qingdao province Jinhong road 266111 No. 88 Applicant after: CRRC QINGDAO SIFANG CO., LTD. Address before: Jihongtan town Chengyang District Shandong city Qingdao province Jinhong road 266111 No. 88 Applicant before: CSR Qingdao Sifang Locomotive and Rolling Stock Co., Ltd. |
|
| COR | Change of bibliographic data | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140910 |
|
| RJ01 | Rejection of invention patent application after publication |